ABSTRACT
Crystalline nanowhiskers (NWs) composed of fullerene C60 and C70 molecules, i.e., alloy NWs, were synthesized by a liquid-liquid interfacial precipitation method. The nominal composition of C70 ranged from 0 to 40 mass%. The bending tests of the alloy NWs were performed inside a high-resolution transmission electron microscope, and the deformation behavior was observed in situ. The bending force acting on the NWs were measured simultaneously by an optical deflection method, and the Young's modulus was estimated from the resulting force-flexure curves. The average Young's modulus was found to increase to approximately 30 GPa as the C70 composition was increased to the solubility limit. In contrast, the Young's modulus decreased with increasing NW diameter caused by the addition of C70.
ABSTRACT
Through various in situ analyses, we have revealed the structural changes that occur during the reversible melting-solidification process of layered alkylsiloxanes (CnLSiloxanes) with carbon numbers (n) of 18 and 16. In situ high-resolution solid-state (13)C nuclear magnetic resonance (NMR) analysis at controlled temperatures indicates drastic conformational changes of the long alkyl chains during the melting-solidification process. A (13)C NMR signal at 33 ppm, which shows the highest intensity at room temperature (RT), is assigned to an inner methylene group with an all-trans conformation. As the temperature increases, the 33-ppm signal intensity decreases while the signal intensity at 30.5 ppm simultaneously increases. The 30.5 ppm signal is assigned to an inner methylene group with a trans-gauche conformation. Subsequently, upon cooling, the signal at 33 ppm recovers, even after CnLSiloxanes have melted. In situ X-ray diffraction measurements at controlled temperatures reveal that the ordered arrangement of the long alkyl chains becomes disordered with elevating temperatures and reordered upon cooling to RT. In situ high-resolution solid-state (29)Si NMR analysis shows that the melting-solidification process progresses without any structural change in siloxane sheets of the CnLSiloxanes. Thus, the in situ analyses show that disordering of the long alkyl chains causes the CnLSiloxanes to melt. Because the majority of long alkyl chains are packed again in the ordered arrangement with the all-trans conformation upon cooling, the CnLSiloxanes are reversibly solidified and the CnLSiloxane structure is recovered.